Method for vapor phase treatment of petroleum distillates



Feb. 15, 1938.

METHOD FOR VAPOR PHASE TREATMENT OF PETROLEUM DlSTILLATES 6A SOL/fvg VA poes H. s. MONTGOMERY 2,108,690

Filed March 50, 1932 3 Shets-Sheet l @de/75er .15 9. Z'

Of/ TL ET INVENTOR. ,fz ffy Ljfolzgo magy,

ATTORNEYS Feb. 15, 1938.

METHOD FOR VAPOR PHASE TREATMENT OF PETROLEUM DlSTILLATES GRA/VIM A R MA TEK/A L Can/pinyin Pur/fk5 0am fr H. S. MONTGOMERY Filed March 30, 1932 5 Sheets-Sheet 2 ATTORNEYS Feb. 15, 1938. H. g; MONTGOMERY 2,108,690

METHOD FOR VAPOR PHASETREATMENT OF PETROLEUM DlsTILLATES 5 Sheets-Sheet 3 Filed March 30, 1932 (MRW/VG Do o f? Y M C R M U 5 l E a M m m H s L Hmmm m/W 5 am 5 Mw i w 0 c JPf/v CLAY METHOD FR VMPR PHASE TREATMENT! @1F lPE'llRLElUM DHS'EHLLA'ELIES lHenry S. Montgomery,

assigner oi one-bali to Alfred W.

Marino, Dalit South Pasadena, aiiil.,

Knight, San

imitation Mms so, i932, serai No. toaosc 5 Claims.

The present invention relates to the puriication of hydrocarbon vapors, such as cracked" or straight-run lpetroleum distillates by the use of an adsorbent polymerizing agent, such as decolorizing or bleaching clay, fullers earthor the like, and particularly to a method for the treatment of such petroleum distillates in the vapor-phase.

'I'he principal object of the present inventio-n is to provide a method for the vapor-phase treatment of petroleum distillates with the use of an adsorbent material, in 'such manner that the undesirable relatively high boiling-point liquid polymerization products formed during such treatment are rapidly and eillciently removed y,

is occluded by said polymers, preventing access from the adsorbent so as to preserve the latter in an active condition for as long a period as possible, whereby the relative emciency of such adsorbent polymerizing agent is materially increased.

One of the major objectsv of the invention is to provide a method for the above-mentioned purpose, wherein the polymers formed by the contact of petroleum vapors with the solid adsorbent polymerizing agent are allowed to drain from said agent through a relatively short path as compared with the minimum length of path of the vapors through said agent, whereby said polymerizing agent is maintained relatively clean of such polymers during such treatment, and the effective life and eiilciency thereof arev materially increased.

A further major object of the present invention is to provide a method for the above-mentioned purpose in which petroleum distillate vapors are caused to pass through a body of ad sorbent polymerizing agent in such manner that the path of such vapors through said body is of relatively greater length than the maximum vertical thickness of said body', and in which the condensed polymers formed by contact of sa.id`

(im. litt-96) Nos. 1,759,8l2f-3-4, the adsorbent material is disposed in a vertical container or treating chamber.A and the petroleum distillates or vapors are passed downwardly through the adsorbent mass. The contact of the vapors with the adsorbent results in the formation of heavy, resinous liquid polymerization products which, due to the washing action oi the vapor stream, are washed downwardly through the adsorbent mass. A natural result of this arrangement is that the polymers are in contact with lthe adsorbent material through substantially the same path as that taken by the vapors passing through said adsorbent mass, and hence under some conditions, a relatively large proportion of the adsorbent theretoby the vapors.

According to the method of treating vapors of petroleum distillates as set forth in this invention, the adsorbent polymerizing agent' may be disposed in an elongated chamber or container and the distillate vapors passed longitudinally through the chamber. The polymers formed by the action oi the adsorbent agent on certain constituents present in the vapors are allowed to drain vertically downwardly to the lower wall of the chamber, through a relatively short path as .\-compared with the path taken by the vapors be removed in any suitable manner. The chamn ber is preferably disposed at a relatively -large angle with respect to the vertical, such angle being preferably but a little less than the complementary angle of the angle of repose of the particular adsorbent material in use, and may ordinarily be in the neighborhood of 60, wherev.by the adsorbent agent may be removed from -the container by gravity upon necessity.

In the method of the present invention, petroleum distillate vapors are caused to pass through a body of adsorbent polymerizing agent characterized by the property of causing polymerization of certain constituents of said vapors, and'saidl body of adsorbent polymerizing agent is disposed at an angle to the vertical and of such dimensions and proportions with respect to said angle of disposition as to cause the maximum .length of path through which the condensed `liquid polymers drain downwardly therethrough /to be materially less than the minimum length of path of said vaporsthrough said body, and preferably less' than one-half. the length of said minimum vapor path.

The method of the present invention may also comprise, if desired. the washing of the body of passing throughthe chamber, whence they may adsorbent polymerizing agent by means of a quantity of treated gasoline or -other suitable solvent, concurrently with the passage of the vapors through said body, whereby the condensed polymers are continuously washed from the adsorbent body and drained, together with the washing solvent, from the treating chamber. When such a. procedure is followed, the mixture of solvent and polymers may advantageously be subjected toA a distillation process whereby the solvent may be returned for further washing action,and the polymers withdrawn to waste or salvage as desired. K

The method of the present invention may. be carried out in an elongated container of circular or other suitable cross-section and a body l of adsorbent polymerizing agent within said container, said container being provided with vapor ingress and egress means at oppositeends of said body of material, polymerizing agent charging and discharging means and condensed polyvmer discharging means, said container being of The accompanying drawings illustrate'severaliv embodiments of apparatus in which the method of the present invention may be practiced, and

referring thereto:

Fig. 1 is a side elevation of a preferred form of apparatus, showing an inclined treating chamber provided with a reflux polymer washing arrangement;

Fig. 2 is a transverse section thereof on line 2-2 in Fig. 1;

Fig. 3 is a sectional side elevation of any alternative form of treating chamber, showing one form of drain for the condensed polymers;

. Fig. 4 is a,transverse section thereof on line 4-4 in Fig. `3;

Fig. 5 is a sectional view corresponding to that shown in. Fig. 4, showing an alternative form of condensed polymer drain;

Fig. 6 is a longitudinal section of another alternative form`of treating chamber, provided with mechanically operable means for removal of spent adsorbent material;

Fig. '7y is a transverse section thereof on 1--1 in Fig. 6;

Fig. 8 is a longitudinal elevation of a. form of apparatus adapted for continuous operation, ailowing of intermittent charging and discharging of fresh and spent vportions of the adsorbent poiymerizing agent, a portion of said container being broken away to show the interior detail;

une

Fig. 9 is a diagrammatic representation of the' proportional relations of the diameter and length of the reaction chamber of the present invention. with relation to the angle of disposition thereof.

Referring to the drawings, there is shown in Figs. l and'2 a form of apparatus embodying the primary principles of the process functions, wherein an elongated chamber I, of cylindrical or ,other 'suitable shape, is provided with distillate vapor pipes 2a and'2b', a charging door 4 and a discharging door 5 for the purpose of filling petroleum vapors, with the formation of resinous compounds of higher molecular weight, hereinaft-er termed polymers, upon contact therewith. said polymers being normally liquid at the temperatures involved in the vapor treatment.

A .plurality of pipes 6, provided with valves 1, are shown as extending from the lower wall of the chamber i providing communication between said chamber and a manifold or header 9. The manifold a may bev provided with a heating jacket, as shown, if desired and may comprise an inner tubular member II in communication with the lower ends of the pipes 6 and provided at its lower end with an outlet connection I2 through which the condensed polymers may be drained. 'Ihis outlet may be provided with a suitable seal or trap such as shown at I3, if desired. The upper end of the member II may be connected to a condenser I5 'through a pipe I4. The manifold 9 may further comprise an outer tubular member I Ia surrounding the member II and providing an annular space I6 through which steam or other `heating agent may be passed, connections for the inlet and exhaust 0I such agent being `,shown at I1. A drain connection may be provided for the manifold, as shown at I8, if desired. v

Suitable means are provided in thisform of device/for washing the condensed polymers from the adsorbent clay, said clay being shown diagrammatically at I9 in Fig. 2. Such means may comprise a header 2I provided with a plurality of perforated pipes 2Ia disposed in the. upper portion of the chamber I and provided with suitable connection to a source of solvent supply,

as indicated at 22. It is preferable that the' chamber I-be provided with suitable insulation, not shown, surrounding the chamber I, the manifold l9 and the inletl and outlet vapor lines 2,

such insulation being for the purpose of maintaining the temperature within the chamber I and the vapor lines sufilciently elevated so that substantially no condensation of the vapors is realizedfater the manner of common practise.

Accordingto the method of the present invention, the operation of the form of apparatus above described may be as follows': Thechamber I is filled with a suitable clay through door 4 .and petroleumY distillatev vapors are passed through the chamber through the pipes 2a and '212, it beingimmaterial to the broaderI aspects of the present invention whether said vapors are caused to move upwardly through the body of adsorbent material -or downwardly therethrough. Upon contact of thel vapors with the'clay, polymerization of certain constituents of the vapors is effected, and the polymers thus formed are deposited upon the clay,and after suiiicient accumulation will drain downwardly through the mass. The polymers may thus drain downwardly from their points of formation to the bottom wall I a of the chamber I, and will thence drain downwardly along said wall to one of the pipes 6, and

thence be conducted through said pipe to the paratus, the maximum path along which portions of the condensed polymers may drain (such as is shown, for example, by the dotted line d) is materially less than the minimum vapor path (shown by the dotted line p) It will be seen, also, that the length of this maximum polymer path as compared with the length of the minimum vapor path is a function of the diameter, length and angle of inclination of the clay body. Referring to Fig; 9, the chambers shown diagrammatically at A30", B50 and C70", represent three containers lled with clay, eachlhaving the same length. of minimum vapor path (represented by the lines Vp) and the same length of maximum polymer path (represented by the line Pp), but having different angles of inclination, as designated. In this case, it will be seen that in order to preserve the relation of the paths Vp and Pp as found in A30, it is necessary to reduce the diameter of the container 070 to about 40%. of the'diameter of that of A30". It will thus be understood that the length and diameter of the container or the clay body will be of such proportion with respect to the angle of disposition thereof that the prescribed relation between the lengths of the re- I have f spectve paths aforesaid is obtained. found that, when the length of the minimum vapor path is caused to be in the neighborhood of or in excess of twice the length of the maximum polymer path, a very advantageous relationship exists, obtaining operation ofthe a'pparatus in such manner that the adsorbent polymerizing agent is maintained at high eciency for a comparatively long period.`

The expression maximum path of condensed A polymers is used to denote,.in general, the length of av vertical path through the body of adsorbent having the greatest length. i It will be understood that, in some cases, for example when the petroleum vapors are admitted to the treating chamber through the pipe 2B and withdrawn through the pipe 2b, there will be a slight washing action of said Yvapors on the condensed polymers, tending to cause the same to drain through a path at some angle tothe vertical, such as ls indicated by the dotted line d1, which will be slightly longer than the vertical drain path d. On the other hand, if the vaporsv are passed through the treating chamber in an upward direction from 2b to 2a, the condensed polymers Will be caused to drain through some such path as is shown by the dotted line d2, somewhat sh'orter than the vertical path d. In this latter manner"'eifective removal of the condensed polymerization products is obtained of the vertical drainage path.

through a path materially shorter than the length When it is desired to effect washing of the adsorbent body by the use of a solvent, such solvent may be suppliedto the header 2l and caus'ed to percolate downwardly through the adsorbent mass, washing the polymers with it, and then withdrawn from the chamber throughthe pipes 6 into the member Il. Steam or other heating agent may be supplied to the space lE surrounding said member and the mixture of polymers and solvent may be subjected `to a distillation whereby the solvent, being of lower boiling point than the polymers, is vaporized and deliveredr to the condenser I5 through the pipe I4. The condensed solvent may then be returned to the header 2i through the pipes 24 for further washing, and the polymers which have been substantially freed of After a period oi time, the adsorbent polymerizing agent or clay will become vitiated and will no longer eectively obtain formation of polymers, upon which the flow of vapors through the chamber may be stopped, the clay discharge door 5 opened, the spent clay removed and said discharge door closed. The chamber may then be charged with fresh clay through the door l and the operation repeated.

I have found it advisable to provide the pipes ii with a column of granular material such as shown at ta, supported on screens 6b, so'that washing of the adsorbent material from the chamber into the header t will be prevented. Such granular material may comprise relatively coa"rsely crushedquartz, sand or the like, which may serve in the manner of a lter.

In the form of apparatus shown in Figs. 3 and 4, the treating chamber 25 is provided with an alternative form of polymer drain, which may comprise a channel or trough 26 secured to the lower wall of the chamber in any suitable manner as, 'for example, by welding, the portion 25a of the chamber wall immediately above the said trough being suitably perforated to allow passage of liquid from the interior of said chamber into said trough. The trough 26 may be provided at its upper and lower ends with charging and cleanout doors 2li, as shown, and the lower end is provided with a condensed polymer drain 28 provided with a seal 23. The trough 2t is preferably filled with ua relatively coarse granular material whereby 'short-circuiting of the vapors therethrough is'prevented. This form of apparatus is not shown as provided-with a solvent .reflux arrangement, such as shown in Figs. 1 and 2, though it will be appreciated that it may be so provided, ifdesired.

Fig. 5 shows a chamber 3l? provided with a modified form of polymer drain, formed by a plurality of overlapping spaced slats 3i extending longitudinally of the chamber and adjacent the bottom Wall thereof and dening a space 32, to which passage of the adsorbent material 33 is prevented by virtue of said slats, and through which the condensed polymers may flow. Suitable means may be provided at desired points along the bottom wall of the chamber below the space 32, or at the lower end of the chamber for removal of the condensed polymers. Also, the space 32 may be filled with a granular material as above described. if desired.

Figs. 6 and '7 show at 33 an alternative form of treating chamber adapted to be disposed substantially horizontally with respect to the flow of vapors therethrough. lyleans are provided at either end of the chamber for ingress and egress of vapors, as shown at 34. Suitable charging 1 doors or ports 35 are provided at the upper side of the chamber, and the form of clay removal means herein shown may comprlsea screw-conveyor formed of two halves 36" and 31, right and left hand, respectively, said conveyor being mounted for rotation in a longitudinal trough or well 38 open to communication throughout its length with the interior of the chamber 33 at 'the bottom thereof.v -A claydischarge door 39 is not shown, and the clay present within the chamber 33 is thus drawn inwardly through the trough 38 towards the discharge door 39, the clay present in the chamber being allowed to fall-freely intos'aid trough. A suitable drain connection may be provided as at 4I for the withdrawal of the condensed polymers.

The form of apparatus shown'in Fig. 8 is adapted for intermittent charging of fresh and discharging of spent portions of clay without interruption of the flow of vapors through the chamber. AAs an illustration, I have shown a form of treating chamber such as above described and shown in Figs. 3 and 4, with the exception that a clay charger and dischargenhave been substituted for the charging and discharging doors. .The clay charger may comprise a container 42 of any convenient dimensions and shape, provided with an upper valve 43 and a lower valve iii and the discharger t5, which pref-,- erably is of the same cubical content as the charger 42, is provided with a similar valve arrangement, as shown at 45 and di. The clay charger i2 may be provided with direct oonnection to a clay bin de, as shown, or may bo provided with a suitable hopper at the upper end thereof into which the clay may be dumped upon occasion.

In the operation of the above-described form of apparatus, assuming the chamber to be filled with clay, and the valves 43, llt, lo and il to be closed, a flow of vapors is kestablished therethrough. Upon the clay becoming somewhat vitiated, the valve :i3 may be opened@ and the charger l2 "filledwith clay from said bin, the

vvalve @i3 is then closed, and the valves M and it opened, allowing a measured portion of the adsorbent material to ow outwardly of the chamberhinto the discharger (i5. At the same time, the clay will flow from the charger i2 into the chamber', replacing the clay withdrawn. The

valves i4 and 46 are then closed and the valve lll opened, discharging the portionl of spent clay to Waste or treatment for recovery, as desired.

-in the amount of clay consumed in the treating operation, and at the same time more uniform treating results may be obtained, in that the vapors treated according tothe above described method are consistently of' optimum desired` purity.

It will be understood that the reluxing of a washing solvent through the clay body may be incorporated in any of the above described modifications of the apparatus and that the continuous operation feature of the latter form may advantageously be incorporated in any of the previously described forms. y

It will be further understood that nthe oondensed 'polymers may be allowed to drain along the lower wall of the chamber and withdrawn at the lower end thereof in any suitable manner, without departing from the spirit of the invention, as, for the purposes of this invention, it is immaterial how the polymers are removed irom the container. v-

It will be .readily seen that the present invention is adapted for multiple installation, such as. for example, a plurality of relatively long tubular treating chambers disposed at a suitable angle to the vertical and provided with a. clay charging manifold at one end and a clay discharging manifold at the other end, vapor ingress and egress means and condensed polymer withdrawing means.

I claim:

l. The method of purifying hydrocarbon vaporsv which comprises passing such vapors through a body of adsorbent polymerizing agent to cause polymerization oi' 'certain constituents of saidr vapors to form liquid polymers, said vaporsbeing ,caused to pass through said adsorbent body in such manner as to Ycause said liquid polymers to drain from said body through paths shorter than the vertical free-fall path of the polymers and- 2. The invention set forth in claim l, said body being of such proportions and dimensions with respect to the angle of disposition thereof as to cause said polymers to drain from said body along paths having a. maximum length materially less than the minimum length of path.' of said vapors through said body.

3. A process for rening hydrocarbon vapors which comprises passing the same in a direction having a substantial horizontal component through a treating zone elongated in said direction containing a bed of polymerizing agent and having a space maintained free of solid in the lower portion thereof, the bottom of said bed being inclinedupwardly in the direction of flow of the vapors through the treating zone, exposing the `vapors to contact with the polymerizing agent during their flow through the treating zone, permitting resultant liquid products to ldrain downwardly byl gravity from said 4bed into said space in the lower portion of the treating zone, and removing the liquid products ffrom said space.

d. A process for reilning hydrocarbon vapors which comprises passing the vapors in a `direction having a substantial horizontal component through a bed of polymerizing agent elongated in said direction and inclined to `the horizontal,

.thereby forming liquid polymers, and draining the liquid polymers from said bed downwardly along Hpaths at an angle to the vertical and shorter than the vertical free-fall path of the polymers.

Y 5. .Av process for refining hydrocarbon vapors which comprises introducing the vapors into an elongated, horizontally inclined bed of polymervizing agent, passing the vapors lengthwise through said bed inY the direction of upward in clination of the bed, and draining resultant liquid 

